US4828819A - Compositions containing bis-(quaternary ammonium) derivatives for the treatment of keratin materials and natural non-keratin or synthetic textile materials - Google Patents

Compositions containing bis-(quaternary ammonium) derivatives for the treatment of keratin materials and natural non-keratin or synthetic textile materials Download PDF

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Publication number
US4828819A
US4828819A US07/207,624 US20762488A US4828819A US 4828819 A US4828819 A US 4828819A US 20762488 A US20762488 A US 20762488A US 4828819 A US4828819 A US 4828819A
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hair
composition
composition according
denotes
quaternary ammonium
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US07/207,624
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Gerard Land
Serge Forestier
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LOreal SA
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LOreal SA
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Priority claimed from FR8018711A external-priority patent/FR2489324A1/en
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    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q5/00—Preparations for care of the hair
    • A61Q5/12—Preparations containing hair conditioners
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/40—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing nitrogen
    • A61K8/41—Amines
    • A61K8/416—Quaternary ammonium compounds
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q5/00—Preparations for care of the hair
    • A61Q5/02—Preparations for cleaning the hair
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C275/00—Derivatives of urea, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups
    • C07C275/04—Derivatives of urea, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups having nitrogen atoms of urea groups bound to acyclic carbon atoms
    • C07C275/06—Derivatives of urea, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups having nitrogen atoms of urea groups bound to acyclic carbon atoms of an acyclic and saturated carbon skeleton
    • C07C275/14—Derivatives of urea, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups having nitrogen atoms of urea groups bound to acyclic carbon atoms of an acyclic and saturated carbon skeleton being further substituted by nitrogen atoms not being part of nitro or nitroso groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D273/00—Heterocyclic compounds containing rings having nitrogen and oxygen atoms as the only ring hetero atoms, not provided for by groups C07D261/00 - C07D271/00
    • C07D273/02—Heterocyclic compounds containing rings having nitrogen and oxygen atoms as the only ring hetero atoms, not provided for by groups C07D261/00 - C07D271/00 having two nitrogen atoms and only one oxygen atom
    • C07D273/04—Six-membered rings
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/322—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing nitrogen
    • D06M13/46—Compounds containing quaternary nitrogen atoms
    • D06M13/467—Compounds containing quaternary nitrogen atoms derived from polyamines
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q5/00—Preparations for care of the hair
    • A61Q5/04—Preparations for permanent waving or straightening the hair
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q5/00—Preparations for care of the hair
    • A61Q5/06—Preparations for styling the hair, e.g. by temporary shaping or colouring
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q5/00—Preparations for care of the hair
    • A61Q5/08—Preparations for bleaching the hair
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q5/00—Preparations for care of the hair
    • A61Q5/10—Preparations for permanently dyeing the hair
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S424/00—Drug, bio-affecting and body treating compositions
    • Y10S424/01—Aerosol hair preparation
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S424/00—Drug, bio-affecting and body treating compositions
    • Y10S424/04—Dandruff

Definitions

  • the present invention relates to compositions containing bis-(quaternary ammonium) derivatives, for the treatment of keratin materials, such as hair, skin, nails and wool, and of natural non-keratin or synthetic textile materials, and to compounds used in these compositions.
  • compositions used in particular as post-shampoo rinsing products, are usually presented in the form of milky liquids, balms or creams and have the disadvantage of weighing down the hair treated, both because of the nature of the quaternary ammonium derivatives used and because of the nature of the adjuvants required to give these compositions the desired appearance, viscosity and softness effects. Because of their weighing-down effect, these compositions are preferably used in the treatment of dry or damaged hair.
  • compositions for use in the treatment of keratin materials and natural non-keratin or synthetic textile materials which compositions generally constitute limpid, fluid or optionally thickened formulations, and that these compositions, when applied to any type of hair (dry hair, normal hair or hair which tends to become greasy), give the hair more lightness than the compositions containing the quaternary ammonium derivatives which have so far been used.
  • the compounds can be used in relatively small amounts for improving the comb-out, the softness, the shine, the hold and the bulk of the hair, and are furthermore well tolerated by the skin.
  • lower alkyl radical is to be understood as meaning a C 1 to C 6 alkyl radical.
  • R 1 , R 2 , R 4 and R 5 preferably denote a lower alkyl radical, in particular methyl or ethyl;
  • R 3 preferably denotes an alkyl radical, in particular a C 8 to C 18 alkyl radical; and
  • a 1 and A 2 preferably denote an alkylene radical, in particular ethylene or trimethylene.
  • the present invention also provides a process for the treatment of keratin materials and natural nonkeratin or synthetic textile materials with the aid of the compositions defined above.
  • X preferably denotes a halogen atom.
  • the polycondensation reaction is carried out, for example, in a solvent which assists quaternisation reactions, or in a mixture of such solvents, such as water, dimethylformamide, acetone, methyl ethyl ketone, acetonitrile and lower alcohols, in particular methanol.
  • a solvent which assists quaternisation reactions or in a mixture of such solvents, such as water, dimethylformamide, acetone, methyl ethyl ketone, acetonitrile and lower alcohols, in particular methanol.
  • the reaction temperature is suitably from 10° to 150° C. and preferably from 20° to 100° C., and the reaction time depends on the nature of the solvent and the starting reactants.
  • the compounds corresponding to the formula (I) possess valuable properties when they are used in the treatment of keratin materials, such as hair, skin, nails and wool, and of natural non-keratin or synthetic textile materials.
  • compositions for use in the treatment of the keratin materials and natural non-keratin or synthetic textile materials mentioned above are preferably aqueous compositions, which can be used as such, but which can also contain adjuvants normally used in compositions for the treatment of keratin materials or non-keratin textile materials.
  • compositions according to the invention are applied to the materials indicated above in a sufficient amount and, after an interval of, say, 1 to 30 minutes, the materials are optionally rinsed.
  • the compounds of the formula (I) give particularly valuable results when they are applied in cosmetics and in particular when they are used for treating the hair.
  • compositions are suitably presented in the form of aqueous, alcoholic or aqueous-alcoholic solutions or in the form of creams, gels, emulsions or powders, or can be packaged in an aerosol in the presence of a propellant.
  • the adjuvants optionally present in these compositions are cosmetically acceptable adjuvants such as non-ionic, anionic, cationic or amphoteric surface-active agents which are well known in the state of the art, animal, mineral, vegetable or synthetic oils or waxes, fatty alcohols, anionic, cationic, non-ionic or amphoteric resins normally used in cosmetics, emulsifiers, sun filters, organic solvents, thickeners, opacifiers, preservatives, sequestering agents, anti-oxidants, perfumes, agents for imparting pearlescence, dyestuffs, pH modifiers, reducing agents, electrolytes, oxidising agents, natural substances, protein derivatives, anti-seborrhea or anti-dandruff agents, restructuring agents, and other substances active in the treatment, care or protection of the skin or hair.
  • cosmetically acceptable adjuvants such as non-ionic, anionic, cationic or amphoteric surface-active agents which are well known in the state of the art,
  • compositions can be used, in particular, as shampoos, as colouring or bleaching products, as rinsing lotions to be applied before or after shampooing, before or after colouring or bleaching or before or after perming or as styling or restructuring lotions, treating lotions, in particular anti-seborrhea or anti-dandruff lotions, brushing lotions, hair lacquers, wavesetting lotions, perming compositions, styling gels and hair-care creams.
  • lotions in particular anti-seborrhea or anti-dandruff lotions, brushing lotions, hair lacquers, wavesetting lotions, perming compositions, styling gels and hair-care creams.
  • compositions to the hair are optionally followed by rinsing, after an interval of, say, 1 to 30 minutes.
  • the compounds used in the invention are applied in order to treat the hair, either in pre-treatment or post-treatment lotions or during the treatment, such as shampooing, dyeing, bleaching, wavesetting, or perming, they can substantially improve the properties of the hair by making the hair easier to comb out when wet or dry and by giving the hair hold, shine, softness, suppleness, manageability and antistatic properties when dry.
  • the hair treated in this way is light, bouncy and bulky.
  • the bis-(quaternary ammonium) derivatives of the formula (I) should be used in the compositions according to the invention in sufficient amounts to obtain the desired result, and generally in amounts from 0.01 to 10% by weight and preferably from 0.1 to 5% by weight, relative to the total weight of the composition.
  • the cosmetic compositions for the hair are treating compositions or pre-treatment or post-treatment compositions for the hair, such as rinsing lotions, wavesetting lotions, restructuring lotions, leave-on lotions or hair-care creams.
  • the pH of these compositions is generally from 2 to 11.
  • the treating compositions or pre-treatment or post-treatment compositions can contain various adjuvants, in particular polyethylene glycols and their derivatives, anionic, cationic, amphoteric or non-ionic resins normally used in cosmetic compositions for the hair, pH modifiers, protein derivatives, such as quanternised or unquaternised protein hydrolysates, natural substances, such as plant extracts, fatty alcohols, such as optionally polyoxyethyleneated or polyglycerolated cetyl, stearyl, cetyl/stearyl or oleyl alcohol, animal, vegetable, mineral or synthetic oils or waxes, such as optionally oxyethyleneated vaseline oil (liquid petrolatum), corn oil, wheatgerm oil, olive oil, soya oil, castor oil or avocado oil, active substances, such as anti-seborrhea or anti-dandruff products, hair-restructuring agents, such as methylolated derivatives, and also other cosmetic adjuvants normally
  • the compositions for treating the hair are shampoos which are essentially characterised in that they contain at least one anionic, non-ionic or amphoteric surface-active agent, or mixtures thereof, and a compound of the formula (I), in an aqueous medium.
  • These compositions can also contain various adjuvants normally used in this type of composition, such as cationic surface-active agents, dyestuffs in the case of colouring shampoos, preservatives, thickeners, foam stabilisers, synergistic agents, softeners, sequestering agents, one or more cosmetic resins, perfumes, protein derivatives, natural substances, oils and also other adjuvants used in a shampoo.
  • the concentration of detergent is generally 2 to 50% by weight.
  • non-ionic detergents there may be mentioned, in particular, the condensation products of a monoalcohol, an alpha-diol, an alkylphenol, an amide or a diglycolamide with glycidol, such as the non-ionic surface-active agents described in French Pat. Nos.
  • anionic surface-active agents which can be used, optionally mixed with the non-ionic surface-active agents, are chosen, in particular, from amongst the alkali metal salts, the ammonium salts, the amine salts or the aminoalcohol salts of the following compounds:
  • alkyl-sulphates alkyl-sulphates, alkyl-ether-sulphates, alkylamide-sulphates and alkylamido-ether-sulphates, alkylaryl-polyether-sulphates and monoglyceride-sulphates;
  • alkylsulphonates alkylamindesulphonates, alkylarylsulphonates and ⁇ -olefinesulphonates
  • alkyl-sulphosuccinates alkyl-ether-sulphosuccinates and alkylamide-sulphosuccinates
  • alkyl-sulphoacetates and alkyl-polyglycerolcarboxylates are alkyl-sulphoacetates and alkyl-polyglycerolcarboxylates
  • alkyl-phosphates and alkyl-ether-phosphates
  • alkylsarcosinates alkylpolypeptidates, alkylamidopolypeptidates, alkylisethionates and alkyltaurates, the alkyl radical in all these compounds being a linear chain having 12 to 30 carbon atoms;
  • fatty acids such as oleic, ricinoleic, palmitic or stearic acid, acids derived from copra oil or from hydrogenated copra oil, and carboxylic acids of polyglycol ethers, corresponding to the formula:
  • substituent Alk corresponds to a linear chain having from 12 to 18 carbon atoms and in which n is an integer from 5 to 15. It is also possible to use other anionic detergents which are well known in the state of the art.
  • amphoteric surface-active agents which can be used, there may be mentioned, more particularly, alkylamino monopropionates and dipropionates, betaines, such as N-alkylbetaines, N-alkylsulphobetaines and N-alkylamidobetaines, cycloimidinium compounds, such as alkylimidazolines, and asparagine derivatives.
  • the alkyl group in these surface-active agents preferably has 1 to 22 carbon atoms.
  • the cosmetic compositions according to the invention can also be hair-dyeing compositions such as so-called oxidation dyeing compositions which contain oxidation dyestuff precursors, for example of the para- or ortho-type, and optionally couplers, in a basic medium preferably having a pH of 8 to 11, and which can also contain direct dyestuffs well known in the state of the art, or dyeing compositions for direct or semi-permanent coloration, which contain direct dyestuffs, such as nitro benzene derivatives, azo dyestuffs, anthraquinone dyestuffs, indamines, indoanilines or indophenols.
  • hair-dyeing compositions such as so-called oxidation dyeing compositions which contain oxidation dyestuff precursors, for example of the para- or ortho-type, and optionally couplers, in a basic medium preferably having a pH of 8 to 11, and which can also contain direct dyestuffs well known in the state of
  • compositions for treating the hair can also be bleaching compositions which are in the form of, for example, powders, solutions, emulsions, gellable liquids or creams containing at least one bleaching agent, such as hydrogen peroxide, peroxides or solutions of per-salts (persulphates, perborates or percarbonates), and at least one compound of the formula (I).
  • bleaching compositions which are in the form of, for example, powders, solutions, emulsions, gellable liquids or creams containing at least one bleaching agent, such as hydrogen peroxide, peroxides or solutions of per-salts (persulphates, perborates or percarbonates), and at least one compound of the formula (I).
  • the bleaching compositions are in the form of creams or gellable liquids. These compositions are usually diluted at the time of use with a solution of hydrogen peroxide and/or per-salt and/or peroxide.
  • compositions generally contain an alkalising agent such as ammonia.
  • bleaching compositions can be applied in accordance with conventional techniques.
  • compositions for treating the hair can also be perming compositions.
  • At least one of the reducing or oxidising compositions contains a compound of the formula (I).
  • the reducing compositions contain adjuvants which make it possible to present them in the form of, for example, lotions or a powder to be diluted in a liquid carrier.
  • the pH of these compositions for the first stage of perming is generally from 7 to 10.
  • the reducing compositions generally contain from 0.01 to 10% by weight of compound of the formula (I), and in particular from 0.1 to 5% by weight.
  • the oxidising or neutralising compositions applied in a second stage can contain conventional adjuvants.
  • the compounds of the formula (I) can of course be used in all the cosmetic formulations as additives for giving the hair characteristics of comb-out, softness, shine, lightness, hold and bulk, in addition to the properties which the compositions themselves are intended to give.
  • compositions according to the invention can also be applied to the skin and can be presented in the various forms mentioned above.
  • the bis-(quaternary ammonium) derivatives give the skin a softness to the touch.
  • compositions can contain various cosmetic adjuvants normally used for the skin, and in particular perfumes, dyestuffs, preservatives, sequestering agents, emulsifying agents, thickeners and sun filters.
  • compositions constitute, especially, treating creams or lotions for the hands or face, antisunburn creams, tinted creams, make-up removal milks or lotions, shaving creams, foaming oils or liquids for the bath or shower, or deodorants which can be prepared in accordance with conventional processes.
  • compositions according to the invention can also be used for finishing and rinsing wool and other natural or synthetic textile materials.
  • the compounds according to the invention also possess other valuable properties such as dispersing, emulsifying or flocculating properties.
  • the pH is adjusted to 7.1 with HCl.
  • About 10 cm 3 of this shampoo are applied to a head of hair wetted beforehand. The hair is massaged lightly. It is rinsed with water, a second application is carried out and the hair is massaged vigorously to obtain a copious foam and, after an interval of a few minutes, is rinsed.
  • the hair is easy to comb out when wet. When dry, the hair is shiny, soft to the touch, light and bouncy and has hold and bulk.
  • the pH is adjusted to 7.6 with triethanolamine.
  • the pH is adjusted to 7 with triethanolamine.
  • the pH is adjusted to 6.2 with NaOH.
  • the above lotion is applied to the clean hair.
  • This lotion is suitably spread over the whole head of hair and, after an interval of about 10 minutes, the hair is rinsed very carefully.
  • the hair When wet, the hair is easy to comb out and is soft to the touch.
  • the hair When dry, the hair is soft, shiny, light and not charged with static electricity. It has hold and bulk.
  • the hair is rinsed.
  • the hair is easy to comb out. It has a silky feel. It is set in waves and dried. The hair is shiny, bouncy and has body (volume); it has a silky feel and is easy to comb out.
  • the hair is rinsed.
  • the hair is easy to comb out. It has a silky feel. An ashen light chestnut shade is obtained.
  • the hair is rinsed.
  • the hair When wet, the hair is easy to comb out and has a soft feel.
  • the hair When wet, the hair is easy to comb out and has a silky feel. After drying, it is shiny, has a silky feel and is easy to comb out.
  • the mixture is applied to washed hair which has been towel-dried, and then the hair is set in waves.
  • the hair is easy to comb out and has a soft feel.
  • the hair is shiny and easy to comb out and has a silky feel.
  • This composition is applied to clean wet hair.
  • the hair is set in waves and dried.
  • the hair is shiny and has hold and bulk. It is soft to the touch and easy to comb out.
  • the reducing liquid is applied to wet hair which has been wound onto rollers. It is left to act for 5 to 30 minutes, the hair is rinsed and the neutraliser is applied. The latter is left to act for 5 to 30 minutes and the hair is rinsed again.
  • the hair treated in this way is soft to the touch and easy to comb out.
  • DEHYTON AB 30 30% strength C 12 -C 18 -alkyl-dimethylcarboxymethylammonium hydroxide sold by HENKEL.
  • AROMOX C12 Solution of copra bis-(2-hydroxyethyl)-amine oxide in a water/isopropanol mixture (50/50), sold by AKZO.
  • POLYSORBATE 20 Polyoxyethykleneated (20) sorbitan monolaurate sold by ATLAS.
  • MIRANOL C2M Cycloimidazoline derivative containing 40% of active ingredient, of the formula: ##STR23## sold by MIRANOL.
  • LIPOPROTEOL LCO Mixed sodium and triethanolamine salts of lipoaminoacids obtained by combining lauric acid with aminoacids derived from the total hydrolysis of collagen. Product containing 22% of active ingredient, sold by RHONE POULENC.
  • CELLOSIZE QP 4400H Hydroxyethylcellulose sold by UNION CARBIDE.
  • AMMONYX 4002 Stearyldimethylbenzylammonium chloride sold by FRANCONYX.
  • EUTANOL G 2-Octyldodecanol marketed by HENKEL.
  • MERGITAL OC 30 Oleyl/cetyl alcohol containing 30 mols of E.O., marketed by HENKEL.

Abstract

The composition of the invention comprises, in a medium suitable for the treatment of keratin materials, and natural non-keratin or synthetic textile materials, at least one bis-(quaternary ammonium) derivative having the formula: ##STR1## in which R1, R2, R4 and R5 are identical or different and denote lower alkyl or lower hydroxyalkyl radicals, R3 is an alkyl, cycloalkyl, alkenyl, hydroxyalkyl or optionally substituted aralkyl radical containing a maximum of 20 carbon atoms, A1 and A2, which are identical or different, represent optionally substituted alkylene or arylene radicals which can contain up to 20 carbon atoms, Z=--SO2 -- or --CO--p, in which p=1 or 2, R6 and R7, which are identical or different, are hydrogen atoms or lower alkyl radicals, or alternatively, if Z=--CO--p in which p=1, R6 and R7 can together form a group: ##STR2## R8 and R9 being hydrogen atoms or lower alkyl radicals, and X.sup.⊖ denotes an inorganic or organic anion derived from low molecular weight acids.

Description

This is a divisional of application Ser. No. 751,454 filed July 2, 1985, now U.S. Pat. No. 4,774,075, which is a continuation application of Ser. No. 270,798, filed June 5, 1981, now abandoned.
The present invention relates to compositions containing bis-(quaternary ammonium) derivatives, for the treatment of keratin materials, such as hair, skin, nails and wool, and of natural non-keratin or synthetic textile materials, and to compounds used in these compositions.
It is known to use cosmetic compositions based on quaternary ammonium derivatives for treating the hair.
These compositions, used in particular as post-shampoo rinsing products, are usually presented in the form of milky liquids, balms or creams and have the disadvantage of weighing down the hair treated, both because of the nature of the quaternary ammonium derivatives used and because of the nature of the adjuvants required to give these compositions the desired appearance, viscosity and softness effects. Because of their weighing-down effect, these compositions are preferably used in the treatment of dry or damaged hair.
We have now discovered, according to the present invention, that the use of a particular class of bis-(quaternary ammonium) derivative makes it possible to prepare compositions for use in the treatment of keratin materials and natural non-keratin or synthetic textile materials, which compositions generally constitute limpid, fluid or optionally thickened formulations, and that these compositions, when applied to any type of hair (dry hair, normal hair or hair which tends to become greasy), give the hair more lightness than the compositions containing the quaternary ammonium derivatives which have so far been used.
The compounds can be used in relatively small amounts for improving the comb-out, the softness, the shine, the hold and the bulk of the hair, and are furthermore well tolerated by the skin.
The present invention thus provides compositions suitable for use in the treatment of keratin materials and natural non-keratin or synthetic textile materials, which comprise, in a medium suitable for the treatment of these materials, at least one bis-(quaternary ammonium) derivative having the formula: ##STR3## in which R1, R2, R4 and R5 are identical or different and denote lower alkyl or lower hydroxyalkyl radicals, R3 is an alkyl, cycloalkyl, alkenyl, hydroxyalkyl or optionally substituted aralkyl radical containing a maximum of 20 carbon atoms, A1 and A2, which are identical or different, represent optionally substituted alkylene or arylene radicals which can contain up to 20 carbon atoms, Z=--SO2 -- or --CO--p, in which p=1 or 2, R6 and R7, which are identical or different, are hydrogen atoms or lower alkyl radicals, or alternatively, if Z=--CO--p in which p=1, R6 and R7 can together form a group: ##STR4## R8 and R9 being hydrogen atoms or lower alkyl radicals, and X⊖ denotes an inorganic or organic anion derived from low molecular weight acids, such as a halide anion, for example chloride or bromide, or a nitrate, sulphate, para-toluenesulphonate, methosulphate or ethosulphate anion.
In this specification, the term "lower alkyl radical" is to be understood as meaning a C1 to C6 alkyl radical.
In the compounds of the formula (I) used in the present invention, R1, R2, R4 and R5 preferably denote a lower alkyl radical, in particular methyl or ethyl; R3 preferably denotes an alkyl radical, in particular a C8 to C18 alkyl radical; and A1 and A2 preferably denote an alkylene radical, in particular ethylene or trimethylene.
The present invention also provides a process for the treatment of keratin materials and natural nonkeratin or synthetic textile materials with the aid of the compositions defined above.
The present invention also provides the new compounds having the formula: ##STR5## in which R1, R2, R4 and R5, R3, A1 and A2 and X⊖ have the meanings indicated above for the formula (I), Z'=--SO2 -- or --CO--p, in which p=1 or 2, and R6 and R7, which are identical or different, are hydrogen atoms or lower alkyl radicals, or alternatively, if Z'=--CO--p in which p=1, R6 and R7 can together form a group ##STR6## R8 and R9 being hydrogen atoms or lower alkyl radicals, with the proviso that, if Z'=--CO--p in which p=1, R3 denotes an alkyl or hydroxyalkyl radical containing at least 4 carbon atoms, and if Z'=--CO--p in which p=2, R3 does not denote an aralkyl radical.
The compounds according to the invention, most of which are water-soluble, can be obtained in accordance with a conventional process by the quaternisation of a tertiary diamine of the formula: ##STR7## with a quaternising agent of the formula:
R.sub.3 --X                                                (III)
in which X preferably denotes a halogen atom.
The polycondensation reaction is carried out, for example, in a solvent which assists quaternisation reactions, or in a mixture of such solvents, such as water, dimethylformamide, acetone, methyl ethyl ketone, acetonitrile and lower alcohols, in particular methanol.
The reaction temperature is suitably from 10° to 150° C. and preferably from 20° to 100° C., and the reaction time depends on the nature of the solvent and the starting reactants.
It is possible to react the starting reactants in equimolecular amounts or to use an excess of quaternising agent.
As indicated above, the compounds corresponding to the formula (I) possess valuable properties when they are used in the treatment of keratin materials, such as hair, skin, nails and wool, and of natural non-keratin or synthetic textile materials.
The compositions for use in the treatment of the keratin materials and natural non-keratin or synthetic textile materials mentioned above are preferably aqueous compositions, which can be used as such, but which can also contain adjuvants normally used in compositions for the treatment of keratin materials or non-keratin textile materials.
The compositions according to the invention are applied to the materials indicated above in a sufficient amount and, after an interval of, say, 1 to 30 minutes, the materials are optionally rinsed.
The compounds of the formula (I) give particularly valuable results when they are applied in cosmetics and in particular when they are used for treating the hair.
The cosmetic compositions are suitably presented in the form of aqueous, alcoholic or aqueous-alcoholic solutions or in the form of creams, gels, emulsions or powders, or can be packaged in an aerosol in the presence of a propellant.
The adjuvants optionally present in these compositions are cosmetically acceptable adjuvants such as non-ionic, anionic, cationic or amphoteric surface-active agents which are well known in the state of the art, animal, mineral, vegetable or synthetic oils or waxes, fatty alcohols, anionic, cationic, non-ionic or amphoteric resins normally used in cosmetics, emulsifiers, sun filters, organic solvents, thickeners, opacifiers, preservatives, sequestering agents, anti-oxidants, perfumes, agents for imparting pearlescence, dyestuffs, pH modifiers, reducing agents, electrolytes, oxidising agents, natural substances, protein derivatives, anti-seborrhea or anti-dandruff agents, restructuring agents, and other substances active in the treatment, care or protection of the skin or hair.
These compositions can be used, in particular, as shampoos, as colouring or bleaching products, as rinsing lotions to be applied before or after shampooing, before or after colouring or bleaching or before or after perming or as styling or restructuring lotions, treating lotions, in particular anti-seborrhea or anti-dandruff lotions, brushing lotions, hair lacquers, wavesetting lotions, perming compositions, styling gels and hair-care creams.
The application of these compositions to the hair is optionally followed by rinsing, after an interval of, say, 1 to 30 minutes.
If the compounds used in the invention are applied in order to treat the hair, either in pre-treatment or post-treatment lotions or during the treatment, such as shampooing, dyeing, bleaching, wavesetting, or perming, they can substantially improve the properties of the hair by making the hair easier to comb out when wet or dry and by giving the hair hold, shine, softness, suppleness, manageability and antistatic properties when dry. The hair treated in this way is light, bouncy and bulky.
The bis-(quaternary ammonium) derivatives of the formula (I) should be used in the compositions according to the invention in sufficient amounts to obtain the desired result, and generally in amounts from 0.01 to 10% by weight and preferably from 0.1 to 5% by weight, relative to the total weight of the composition.
According to a first embodiment of the invention, the cosmetic compositions for the hair are treating compositions or pre-treatment or post-treatment compositions for the hair, such as rinsing lotions, wavesetting lotions, restructuring lotions, leave-on lotions or hair-care creams.
The pH of these compositions is generally from 2 to 11. The treating compositions or pre-treatment or post-treatment compositions can contain various adjuvants, in particular polyethylene glycols and their derivatives, anionic, cationic, amphoteric or non-ionic resins normally used in cosmetic compositions for the hair, pH modifiers, protein derivatives, such as quanternised or unquaternised protein hydrolysates, natural substances, such as plant extracts, fatty alcohols, such as optionally polyoxyethyleneated or polyglycerolated cetyl, stearyl, cetyl/stearyl or oleyl alcohol, animal, vegetable, mineral or synthetic oils or waxes, such as optionally oxyethyleneated vaseline oil (liquid petrolatum), corn oil, wheatgerm oil, olive oil, soya oil, castor oil or avocado oil, active substances, such as anti-seborrhea or anti-dandruff products, hair-restructuring agents, such as methylolated derivatives, and also other cosmetic adjuvants normally used in cosmetic compositions for the hair.
According to a preferred embodiment, the compositions for treating the hair, according to the invention, are shampoos which are essentially characterised in that they contain at least one anionic, non-ionic or amphoteric surface-active agent, or mixtures thereof, and a compound of the formula (I), in an aqueous medium. These compositions can also contain various adjuvants normally used in this type of composition, such as cationic surface-active agents, dyestuffs in the case of colouring shampoos, preservatives, thickeners, foam stabilisers, synergistic agents, softeners, sequestering agents, one or more cosmetic resins, perfumes, protein derivatives, natural substances, oils and also other adjuvants used in a shampoo. In these shampoos, the concentration of detergent is generally 2 to 50% by weight.
Amongst the non-ionic detergents, there may be mentioned, in particular, the condensation products of a monoalcohol, an alpha-diol, an alkylphenol, an amide or a diglycolamide with glycidol, such as the non-ionic surface-active agents described in French Pat. Nos. 2,091,516, 2,328,763 and 1,477,048, and also polyoxyethyleneated or polyglycerolated fatty alcohols, alkylphenols or acids with linear fatty chains having 8 to 30 carbon atoms and most frequently containing 2 to 30 mols of ethylene oxide, copolymers of ethylene oxide and propylene oxide, condensates of ethylene oxide and propylene oxide with fatty alcohols, polyoxyethyleneated fatty amides, polyoxyethyleneated fatty amines, ethanolamides, fatty acid esters of glycol, fatty acid esters of sorbitol and fatty acid esters of sucrose.
The anionic surface-active agents which can be used, optionally mixed with the non-ionic surface-active agents, are chosen, in particular, from amongst the alkali metal salts, the ammonium salts, the amine salts or the aminoalcohol salts of the following compounds:
alkyl-sulphates, alkyl-ether-sulphates, alkylamide-sulphates and alkylamido-ether-sulphates, alkylaryl-polyether-sulphates and monoglyceride-sulphates;
alkylsulphonates, alkylamindesulphonates, alkylarylsulphonates and α-olefinesulphonates;
alkyl-sulphosuccinates, alkyl-ether-sulphosuccinates and alkylamide-sulphosuccinates;
alkyl-sulphosuccinamates;
alkyl-sulphoacetates and alkyl-polyglycerolcarboxylates;
alkyl-phosphates and alkyl-ether-phosphates; and
alkylsarcosinates, alkylpolypeptidates, alkylamidopolypeptidates, alkylisethionates and alkyltaurates, the alkyl radical in all these compounds being a linear chain having 12 to 30 carbon atoms; and
fatty acids, such as oleic, ricinoleic, palmitic or stearic acid, acids derived from copra oil or from hydrogenated copra oil, and carboxylic acids of polyglycol ethers, corresponding to the formula:
Alk--(OCH.sub.2 --CH.sub.2).sub.n --OCH.sub.2 --CO.sub.2 H
in which the substituent Alk corresponds to a linear chain having from 12 to 18 carbon atoms and in which n is an integer from 5 to 15. It is also possible to use other anionic detergents which are well known in the state of the art.
Amongst the amphoteric surface-active agents which can be used, there may be mentioned, more particularly, alkylamino monopropionates and dipropionates, betaines, such as N-alkylbetaines, N-alkylsulphobetaines and N-alkylamidobetaines, cycloimidinium compounds, such as alkylimidazolines, and asparagine derivatives. The alkyl group in these surface-active agents preferably has 1 to 22 carbon atoms.
The cosmetic compositions according to the invention can also be hair-dyeing compositions such as so-called oxidation dyeing compositions which contain oxidation dyestuff precursors, for example of the para- or ortho-type, and optionally couplers, in a basic medium preferably having a pH of 8 to 11, and which can also contain direct dyestuffs well known in the state of the art, or dyeing compositions for direct or semi-permanent coloration, which contain direct dyestuffs, such as nitro benzene derivatives, azo dyestuffs, anthraquinone dyestuffs, indamines, indoanilines or indophenols.
The compositions for treating the hair, according to the invention, can also be bleaching compositions which are in the form of, for example, powders, solutions, emulsions, gellable liquids or creams containing at least one bleaching agent, such as hydrogen peroxide, peroxides or solutions of per-salts (persulphates, perborates or percarbonates), and at least one compound of the formula (I).
Preferably, the bleaching compositions are in the form of creams or gellable liquids. These compositions are usually diluted at the time of use with a solution of hydrogen peroxide and/or per-salt and/or peroxide.
These compositions generally contain an alkalising agent such as ammonia.
These bleaching compositions can be applied in accordance with conventional techniques.
The compositions for treating the hair, according to the invention, can also be perming compositions.
The formulation of such perming compositions, comprising a reducing composition and an oxidising composition (neutraliser), is known and described in the works on cosmetology, in particular by E SIDI and C ZVIAK Problemes Capillaires (Hair Problems), Paris 1966 (GAUTHIER-VILLARD).
According to the invention, at least one of the reducing or oxidising compositions contains a compound of the formula (I).
Apart from the reducing agent, the reducing compositions contain adjuvants which make it possible to present them in the form of, for example, lotions or a powder to be diluted in a liquid carrier.
The pH of these compositions for the first stage of perming is generally from 7 to 10.
The reducing compositions generally contain from 0.01 to 10% by weight of compound of the formula (I), and in particular from 0.1 to 5% by weight.
Apart from the oxidising agent, the oxidising or neutralising compositions applied in a second stage can contain conventional adjuvants.
The compounds of the formula (I) can of course be used in all the cosmetic formulations as additives for giving the hair characteristics of comb-out, softness, shine, lightness, hold and bulk, in addition to the properties which the compositions themselves are intended to give.
The compositions according to the invention can also be applied to the skin and can be presented in the various forms mentioned above. The bis-(quaternary ammonium) derivatives give the skin a softness to the touch.
In addition to the compounds of the formula (I), such compositions can contain various cosmetic adjuvants normally used for the skin, and in particular perfumes, dyestuffs, preservatives, sequestering agents, emulsifying agents, thickeners and sun filters.
The compositions constitute, especially, treating creams or lotions for the hands or face, antisunburn creams, tinted creams, make-up removal milks or lotions, shaving creams, foaming oils or liquids for the bath or shower, or deodorants which can be prepared in accordance with conventional processes.
The compositions according to the invention can also be used for finishing and rinsing wool and other natural or synthetic textile materials.
It should be noted that the compounds according to the invention also possess other valuable properties such as dispersing, emulsifying or flocculating properties.
The following Examples further illustrate the present invention.
Preparation Examples EXAMPLE 1
46 g of 1,3-bis-(3-dimethylaminopropyl)-urea are dissolved in 100 g of acetone. 105 g of 1-bromodo-decane are added and the mixture is heated under reflux for 7 hours. The reaction mixture is left to cool and is then diluted with 400 cm3 of acetone. The solid is filtered off, washed with acetone and dried under reduced pressure. This yields 87 g of a white product melting at 108° C., which corresponds to the formula: ##STR8##
ANALYSIS: Found: Br.sup.⊖ : 2.77 milliequivalents/gram; quaternary ammonium: 2.82 milliequivalents/gram. Theory: 2.75 milliequivalents/gram.
The following compounds are obtained under the operating conditions summarised in the table below:
EXAMPLE 2 ##STR9## 
______________________________________                                    
Elementary analysis                                                       
               C %    H %       N %  S %                                  
______________________________________                                    
Calculated (1H.sub.2 O)                                                   
               38.64  8.33      10.6 12.12                                
Found          39.15  8.40      10.13                                     
                                     12.41                                
______________________________________
EXAMPLE 3 ##STR10##
ANALYSIS: Found: Br.sup.⊖ : 3.42 milliequivalents/gram; quaternary ammonium: 3.44 milliequivalents/gram. Theory: 3.50 milliequivalents/gram.
EXAMPLE 4 ##STR11##
ANALYSIS: Melting point: softening above 150° C. Found: Br.sup.⊖ : 2.51 milliequivalents/gram; quaternary ammonium: 2.62 milliequivalents/gram; Theory: 2.42 milliequivalents/gram.
EXAMPLE 5 ##STR12##
ANALYSIS: Melting point: 170° C. Found: Br.sup.⊖ : 2.58 milliequivalents/gram; quaternary ammonium: 2.58 milliequivalents/gram. Theory: 2.60 milliequivalents/gram.
EXAMPLE 6 ##STR13##
ANALYSIS: Melting point: 140° C. Found: Br.sup.⊖ : 3.07 milliequivalents/gram; quaternary ammonium: 3.05 milliequivalents/gram. Theory: 3.04 milliequivalents/gram.
EXAMPLE 7 ##STR14##
ANALYSIS: Melting point: 204° C. Found: Br.sup.⊖ : 2.62 milliequivalents/gram; quaternary ammonium: 2.64 milliequivalents/gram. Theory: 2.65 milliequivalents/gram.
EXAMPLE 8 ##STR15##
ANALYSIS: Melting point: 152° C. Found: Br.sup.⊖ : 3.76 milliequivalents/gram; quaternary ammonium: 3.76 milliequivalents/gram. Theory: 3.76 milliequivalents/gram.
EXAMPLE 9 ##STR16##
ANALYSIS: 1H NMR spectrum compatible with the proposed structure.
EXAMPLE 10 ##STR17##
ANALYSIS: Melting point: 130° C. Found: Br.sup.⊖ : 2 milliequivalents/gram; quaternary ammonium: 2.13 milliequivalents/gram. Theory: 2.14 milliequivalents/gram.
EXAMPLE 11 ##STR18##
ANALYSIS: Melting point: 130° C. Found: Br.sup.⊖ : 2.30 milliequivalents/gram; quaternary ammonium: 2.26 milliequivalents/gram. Theory: 2.28 milliequivalents/gram.
EXAMPLE 12 ##STR19##
ANALYSIS: Melting point: 110° C. Found: Br.sup.⊖ : 2.42 milliequivalents/gram; quaternary ammonium: 2.36 milliequivalents/gram. Theory: 2.38 milliequivalents/gram.
EXAMPLE 13 ##STR20##
ANALYSIS: Melting point: 170° C. Found: Br.sup.⊖ : 2.28 milliequivalents/gram; quaternary ammonium: 2.25 milliequivalents/gram. Theory: 2.27 milliequivalents/gram.
______________________________________                                    
Conditions for the preparation of the                                     
compounds described in Examples Nos. 2 to 13                              
        Ratio                                                             
        Quaternising                                                      
                    Amount of                                             
        agent       acetone used,                                         
                                Reaction time                             
Example Ditertiary  in cm.sup.3 per                                       
                                under acetone                             
No.     diamine     mol of amine                                          
                                reflux, in hours                          
______________________________________                                    
2       2           1,875        1                                        
3       2.24        2,000        4                                        
4       2.5         2,000       22                                        
5       2.5         2,000       14                                        
6       2           2,500       33                                        
7       2           6,000       56                                        
8       2           3,300       20                                        
9       2.02        4,650       105                                       
10      2           3,750       22                                        
11      2.2         3,750       32                                        
12      2.5         4,500       19                                        
13      2.5         2,500       31                                        
______________________________________
Composition Examples EXAMPLE 14 Shampoo
The following composition is prepared:
______________________________________                                    
Compound of Example 1     0.5 g                                           
                          (of active                                      
                          ingredient)                                     
Non-ionic surface-active agent                                            
                          5.0 g                                           
based on polyglycerolated (of active                                      
(4.2 mols) lauryl alcohol of the                                          
                          ingredient)                                     
statistical formula:                                                      
 ##STR21##                                                                
Non-ionic surface-active agent                                            
                          10.0 g                                          
of the formula:           (of active                                      
RCHOHCH.sub.2 O[CH.sub.2CHOHCH.sub.2 O] .sub.nH                           
                          ingredient)                                     
R = mixture of C.sub.9 -C.sub.12 alkyl radicals                           
n = 3.5, statistical value                                                
Lauryl diethanolamide     2.0 g                                           
                          (of active                                      
                          ingredient)                                     
Water q.s.p.              100 g                                           
______________________________________
The pH is adjusted to 7.1 with HCl. About 10 cm3 of this shampoo are applied to a head of hair wetted beforehand. The hair is massaged lightly. It is rinsed with water, a second application is carried out and the hair is massaged vigorously to obtain a copious foam and, after an interval of a few minutes, is rinsed.
The hair is easy to comb out when wet. When dry, the hair is shiny, soft to the touch, light and bouncy and has hold and bulk.
EXAMPLE 15 Shampoo
The following composition is prepared:
______________________________________                                    
Compound of Example 4                                                     
                  0.3 g (of active ingredient)                            
Dehyton AB 30     10.0 g                                                  
Aromox C.12       3.0 g (of active ingredient)                            
Copra diethanolamide                                                      
                  2.0 g (of active ingredient)                            
Water q.s.p.      100 g                                                   
______________________________________
The pH is adjusted to 7.4 with NaOH. After application to the hair as indicated in Example 14, similar results are obtained.
EXAMPLE 16 Shampoo
The following composition is prepared:
______________________________________                                    
Compound of Example 5    0.9 g (of active                                 
                         ingredient)                                      
Non-ionic surface-active agent of                                         
                         12.0 g (of active                                
the Formula:             ingredient)                                      
R--CHOH--CH.sub.2 O--[CH.sub.2 CHOH--CH.sub.2 --O] .sub.n--H              
R = mixture of C.sub.9 -C.sub.12 alkyl radicals                           
n = 3.5, statistical value                                                
Polysorbate 20           8.0 g (of active                                 
                         ingredient)                                      
Water q.s.p.             100 g                                            
______________________________________
The pH is adjusted to 6 with NaOH. After application to the hair as indicated in Example 14, analogous results are observed.
EXAMPLE 17 Shampoo
The following composition is prepared:
______________________________________                                    
Compound of Example 2                                                     
                    0.4 g (of active ingredient)                          
Sodium salt of sulphated alkanol                                          
                    25 g                                                  
(C.sub.12 -C.sub.14) oxyethyleneated with 2.2                             
mols of E.O. (ethylene oxide) con-                                        
taining 25% of active ingredient                                          
Miranol C2M (solution containing                                          
                    5.0 g                                                 
40% of active ingredient)                                                 
Copra diethanolamide                                                      
                    2.0 g (of active ingredient)                          
Water q.s.p.        100 g                                                 
______________________________________
The pH is adjusted to 8.1 with lactic acid. After application to wet hair as indicated in Example 14, the same results are obtained.
EXAMPLE 18 Shampoo
The following composition is prepared:
______________________________________                                    
Compound of Example 3                                                     
                    3 g (of active ingredient)                            
Non-ionic surface-active agent based                                      
                    10 g (of active ingredient)                           
on polyglycerolated (4.2 mols) lauryl                                     
alcohol of the statistical formula:                                       
 ##STR22##                                                                
Polyoxyethyleneated lauryl alcohol                                        
                    5 g (of active ingredient)                            
containing 12 mols of E.O.                                                
Lipoproteol LCO      24 g                                                 
Water q.s.p.        100 g                                                 
______________________________________
The pH is adjusted to 7 with lactic acid. After application to wet hair as indicated in Example 14, similar results are obtained.
EXAMPLE 19 Shampoo
The following composition is prepared:
______________________________________                                    
Compound of Example 7 2 g (of active                                      
                      ingredient)                                         
Maypon 4 CT           32 g                                                
Polysorbate 20        8 g (of active                                      
                      ingredient)                                         
Water q.s.p.          100 g                                               
______________________________________
The pH is adjusted to 7.6 with triethanolamine.
After application to wet hair as indicated in Example 14, similar results are observed.
EXAMPLE 20 Shampoo
The following composition is prepared:
______________________________________                                    
Compound of Example 9   2.5 g (of active                                  
                        ingredient)                                       
Miranol C2 M (solution containing 40%                                     
                        13.0 g                                            
of active ingredient)                                                     
Sandopan CTC AC         8.9 g                                             
Water q.s.p.            100 g                                             
______________________________________
The pH is adjusted to 7 with triethanolamine.
After application to wet hair as indicated in Example 14, similar results are observed.
EXAMPLE 21 Shampoo
The following composition is prepared:
______________________________________                                    
Compound of Example 6   1.5 g (of active                                  
                        ingredient)                                       
Sodium lauryl-ether-sulphate                                              
                        20.0 g                                            
containing 30% of active ingredient                                       
Sodium salt of sulphated alkanol(C.sub.12 -                               
                        10.0 g                                            
C.sub.14) oxyethyleneated with 2.2 mols                                   
of E.O., containing 25% of active                                         
ingredient                                                                
NaCl                    1.5 g                                             
Water q.s.p.            100 g                                             
______________________________________
The pH is adjusted to 8.1 with NaOH. After application to wet hair as indicated in Example 14, analogous results are observed.
EXAMPLE 22 Rinsing Lotion
The following composition is prepared:
______________________________________                                    
Compound of Example 5   2.5 g                                             
Cetyl alcohol           5.0 g                                             
Cetyl/stearyl alcohol containing 15 mols                                  
                        3.0 g                                             
of E.O.                                                                   
Cellosize QP 4400 H     0.4 g                                             
Ammonyx 27              2.0 g                                             
Water q.s.p.            100 g                                             
______________________________________
The pH is adjusted to 6.2 with NaOH.
After the hair has been shampooed, rinsed and towel-dried, the above lotion is applied to the clean hair.
This lotion is suitably spread over the whole head of hair and, after an interval of about 10 minutes, the hair is rinsed very carefully. When wet, the hair is easy to comb out and is soft to the touch. When dry, the hair is soft, shiny, light and not charged with static electricity. It has hold and bulk.
EXAMPLE 23 Rinsing Lotion
The following composition is prepared:
______________________________________                                    
Compound of Example 4    1      g                                         
Mixture of cetyl and stearyl alcohols                                     
                         2      g                                         
(50/50)                                                                   
Cetyl/stearyl alcohol containing 15                                       
                         3      g                                         
mols of E.O.                                                              
Cellosize QP 4400 H      0.8    g                                         
Ammonyx 4002             1.5    g                                         
Water q.s.p.             100    g                                         
______________________________________
The pH is adjusted to 5.3 with triethanolamine. After application to clean wet hair as indicated in Example 22, similar results are observed.
EXAMPLE 24 Gel For Oxidation Dyeing
The following composition is prepared:
______________________________________                                    
Triethanolamine lauryl-sulphate containing                                
                          2.5    g                                        
40% of active ingredient                                                  
Eutanol G                 7.5    g                                        
Oleyl diethanolamide      7.0    g                                        
Mergital OC 30            3.0    g                                        
Compound of Example 8     2.5    g                                        
Oleic acid                20.0   g                                        
Benzyl alcohol            10.0   g                                        
96° strength ethyl alcohol                                         
                          10.0   g                                        
22° Be strength ammonia solution                                   
                          18     ml                                       
N,N--Bis-(2-hydroxyethyl)-para-phenylene-                                 
                          1      g                                        
diamine sulphate                                                          
p-Aminophenol             0.4    g                                        
Resorcinol                0.15   g                                        
m-Aminophenol             0.10   g                                        
Alpha-naphthol            0.40   g                                        
Hydroquinone              0.10   g                                        
Ethylenediaminetetraacetic acid                                           
                          0.24   g                                        
Sodium bisulphite solution (d = 1.32)                                     
                          1      ml                                       
Water q.s.p.              100    g                                        
______________________________________
30 g of this carrier are mixed in a bowl with 30 g of hydrogen peroxide (20 volumes). This gives a consistent gel which is pleasant to apply and which adheres well to the hair.
It is applied with the aid of a paintbrush.
After an interval of 30 to 40 minutes, the hair is rinsed.
The hair is easy to comb out. It has a silky feel. It is set in waves and dried. The hair is shiny, bouncy and has body (volume); it has a silky feel and is easy to comb out.
An ashen deep blond shade is obtained.
EXAMPLE 25 Gel For Oxidation Dyeing
The following composition is prepared:
______________________________________                                    
Non-ionic surface-active agent of the formula:                            
R--O[--C.sub.2 H.sub.3 O(CH.sub.2 OH)]--.sub.2 H                          
                          20      g                                       
R = oleyl radical                                                         
Non-ionic surface-active agent of the formula:                            
R--O[--C.sub.2 H.sub.3 O(CH.sub.2 OH)]--.sub.4 H                          
                          20      g                                       
R = oleyl radical                                                         
Oleyl diethanolamide      12      g                                       
Compound of Example 3     3       g                                       
96° strength ethyl alcohol                                         
                          12      g                                       
Butylglycol               1       g                                       
Propylene glycol          2       g                                       
Pentasodium salt of diethylenetriamine-                                   
                          2.5     g                                       
pentaacetic acid (40% of active ingredient)                               
22° Be strength ammonia solution                                   
                          9       ml                                      
1-Amino-4-(2-methoxyethyl)-aminobenzene                                   
                          1.6     g                                       
dihydrochloride                                                           
p-Aminophenol             0.3     g                                       
Resorcinol                0.2     g                                       
m-Aminophenol             0.25    g                                       
5-N--(2-Hydroxyethyl)-amino-2-methylphenol                                
                          0.02    g                                       
1-(2-Hydroxyethoxy)-2,4-diaminobenzene                                    
                          0.02    g                                       
dihydrochloride                                                           
Sodium bisulphite solution (d = 1.32)                                     
                          1       ml                                      
Water q.s.p.              100     g                                       
______________________________________
30 g of this carrier are mixed in a bowl with 30 g of hydrogen peroxide (20 volumes).
This gives a gel which is pleasant to apply and which adheres well to the hair.
It is applied with the aid of a paintbrush.
After an interval of 30 to 40 minutes, the hair is rinsed.
The hair is easy to comb out. It has a silky feel. An ashen light chestnut shade is obtained.
EXAMPLE 26 Hair-Care Cream
The following composition is prepared:
______________________________________                                    
Cetyl alcohol             17     g                                        
Sodium cetyl-/stearyl-sulphate                                            
                          6      g                                        
Cetyl/stearyl alcohol containing 15 mols                                  
                          4      g                                        
of E.O.                                                                   
Oleyl alcohol             4      g                                        
Compound of Example 4     2      g                                        
Water q.s.p.              100    g                                        
______________________________________
30 to 50 g of this cream are applied to clean damp hair which has been towel-dried, care being taken to impregnate the head of hair well.
After an interval of 15 minutes, the hair is rinsed.
When wet, the hair is easy to comb out and has a soft feel.
It is set in waves and dried under a hood. When dry, the hair is easy to comb out and has a silky feel. It is shiny and bouncy.
EXAMPLE 27 Lightening Gel
The following composition is prepared:
______________________________________                                    
Eutanol G                 8      g                                        
Triethanolamine lauryl-sulphate containing                                
                          3      g                                        
40% of active ingredient                                                  
Oleyl diethanolamide      6      g                                        
Hydrogenated tallow amide containing                                      
                          3.5    g                                        
50 mols of E.O.                                                           
Oleic acid                18     g                                        
Compound of Example 2     3      g                                        
96° strength ethyl alcohol                                         
                          15     g                                        
Propylene glycol          12     g                                        
22° Be strength ammonia solution                                   
                          16     ml                                       
Ethylenediaminetetraacetic acid sold                                      
                          0.3    g                                        
under the name TRILON B                                                   
Water q.s.p.              100    g                                        
______________________________________
Before use, 40 g of this formulation are mixed in a bowl with 40 g of hydrogen peroxide (30 volumes).
This gives a gel which is pleasant to apply and which adheres well to the hair. After an interval of 30 to 45 minutes, the hair is rinsed.
When wet, the hair is easy to comb out and has a silky feel. After drying, it is shiny, has a silky feel and is easy to comb out.
On deep chestnut hair, a deep blond is obtained after bleaching.
EXAMPLE 28 Restructuring Lotion
Before use, 0.3 g of dimethylolethylenethiourea is mixed with 20 ml of a solution containing:
______________________________________                                    
Compound of Example 9  1.5    g                                           
Water q.s.p.           100    g                                           
HCl q.s.p.             pH     2.7                                         
______________________________________
The mixture is applied to washed hair which has been towel-dried, and then the hair is set in waves.
The hair is easy to comb out and has a soft feel.
It is set in waves and dried.
The hair is shiny and easy to comb out and has a silky feel.
EXAMPLE 29 Wavesetting Lotion 
______________________________________                                    
Polyvinylpyrrolidone VA S 630 from GAF                                    
                          1.5    g                                        
Compound of Example 4     1      g                                        
Ethyl alcohol q.s.p.      15°                                      
Water q.s.p.              100    ml                                       
______________________________________
This composition is applied to clean wet hair. The hair is set in waves and dried. The hair is shiny and has hold and bulk. It is soft to the touch and easy to comb out.
EXAMPLE 30 Perming Composition 
______________________________________                                    
REDUCING LIQUID                                                           
Thioglycolic acid      8        g                                         
Ammonia q.s.p.         neutralisation                                     
Ammonium bicarbonate   7        g                                         
Pentasodium salt of diethylenetriamine-                                   
                       0.2      g                                         
pentaacetic acid                                                          
Polyoxyethyleneated oleyl ether                                           
                       1        g                                         
containing 20 mols of ethylene oxide                                      
Compound of Example 1  2        g                                         
Perfume                0.3      g                                         
Deionised water q.s.p. 100      ml                                        
NEUTRALISER                                                               
Hydrogen peroxide q.s.p.                                                  
                       8 volumes                                          
                       strength                                           
Stabilizers            0.2      g                                         
Polyoxyethyleneated nonylphenol                                           
                       1        g                                         
containing 9 mols of ethylene oxide                                       
Perfume                0.3      g                                         
Citric acid q.s.p.     pH       3                                         
Deionised water q.s.p. 100      ml                                        
______________________________________
The reducing liquid is applied to wet hair which has been wound onto rollers. It is left to act for 5 to 30 minutes, the hair is rinsed and the neutraliser is applied. The latter is left to act for 5 to 30 minutes and the hair is rinsed again. The hair treated in this way is soft to the touch and easy to comb out.
EXAMPLE 31 Perming Composition 
______________________________________                                    
REDUCING LIQUID                                                           
Thioglycolic acid     5         g                                         
Ammonium bicarbonate  8.5       g                                         
Pentasodium salt of diethylene-                                           
                      0.2       g                                         
triaminepentaacetic acid                                                  
Protein hydrolysate   1         g                                         
Polyoxyethyleneated oleyl ether                                           
                      1         g                                         
containing 20 mols of ethylene oxide                                      
Perfume               0.3       g                                         
Deionised water q.s.p.                                                    
                      100       ml                                        
NEUTRALISER                                                               
Hydrogen peroxide q.s.p.                                                  
                      8 volumes                                           
                      strength                                            
Stabilizers           0.2       g                                         
Polyoxyethyleneated nonylphenol                                           
                      1         g                                         
containing 9 mols of ethylene oxide                                       
Compound of Example 1 1         g                                         
Citric acid q.s.p.    pH        3                                         
Perfume               0.3       g                                         
Deionised water q.s.p.                                                    
                      100       ml                                        
______________________________________
By following the same procedure as in Example 30, analogous results are observed after the perming treatment.
The tradenames used in the examples are explained below.
DEHYTON AB 30: 30% strength C12 -C18 -alkyl-dimethylcarboxymethylammonium hydroxide sold by HENKEL.
AROMOX C12: Solution of copra bis-(2-hydroxyethyl)-amine oxide in a water/isopropanol mixture (50/50), sold by AKZO.
POLYSORBATE 20: Polyoxyethykleneated (20) sorbitan monolaurate sold by ATLAS.
MIRANOL C2M: Cycloimidazoline derivative containing 40% of active ingredient, of the formula: ##STR23## sold by MIRANOL. LIPOPROTEOL LCO: Mixed sodium and triethanolamine salts of lipoaminoacids obtained by combining lauric acid with aminoacids derived from the total hydrolysis of collagen. Product containing 22% of active ingredient, sold by RHONE POULENC.
MAYPON 4 CT: Triethanolamine salt of the condensation product of copra acid and animal protein hydrolysate. Product containing 40% of active ingredient, sold by STEPAN.
SANDOPAN CTC AC: Trideceth-7 carboxylic acid of the formula:
CH.sub.3 --(CH.sub.2).sub.11 --CH.sub.2 --(OCH.sub.2 --CH.sub.2).sub.6 --OCH.sub.2 --COOH,
containing 90% of active ingredient, sold by SANDOZ.
CELLOSIZE QP 4400H: Hydroxyethylcellulose sold by UNION CARBIDE.
AMMONYX 27: Monoalkyltrimethylammonium chloride (alkyl=tallow radical) sold by FRANCONYX.
AMMONYX 4002: Stearyldimethylbenzylammonium chloride sold by FRANCONYX.
EUTANOL G: 2-Octyldodecanol marketed by HENKEL.
MERGITAL OC 30: Oleyl/cetyl alcohol containing 30 mols of E.O., marketed by HENKEL.

Claims (20)

We claim:
1. A composition suitable for treating hair, skin and nails which comprises at least one bis-(quaternary ammonium) derivative having the formula: ##STR24## in which R1, R2, R4 and R5 are identical or different and denote lower alkyl or lower hydroxyalkyl radicals, R3 denotes an alkyl, cycloalkyl, alkenyl, hydroxyalkyl or aralkyl radical containing a maximum of 20 carbon atoms, A1 and A2, which are identical or different, denote alkylene or arylene radicals containing a maximum of 20 carbon atoms, Z denotes --SO2 --, R6 and R7, which are identical for different, represent hydrogen atoms or lower alkyl radicals, and X.sup.⊖ denotes an inorganic or organic anion of a low molecular weight acid, and at least one cosmetic adjuvant selected from non-ionic, anionic, cationic or amphoteric surface-active agents, animal, mineral, vegetable or synthetic oils or waxes, fatty alcohols, anionic, cationic, non-ionic or amphoteric resins, emulsifiers, organic solvents, thickeners, opacifiers, preservatives, perfumes, agents for imparting pearlescence, sequestering agents, antioxidants, pH modifiers, electrolytes, and hair restructuring agents, said bis-(quaternary ammonium) derivative being present in an amount of 0.01 to 10% by weight of said composition.
2. A composition according to claim 1, in which R1, R2, R4 and R5 denote a methyl or ethyl radical.
3. A composition according to claim 1 in which R3 denotes a C8 to C18 alkyl radical.
4. A composition according to claim 1 in which A1 and A2 denote an ethylene or trimethylene radical.
5. A composition according to claim 1 for use in the treatment of the hair which is in a form selected from the group consisting of an aqueous, alcoholic or aqueous-alcoholic solution, a cream, a gel, an emulsion, a powder and a product packaged in an aerosol.
6. A composition according to claim 5 which is in the form of an aqueous solution.
7. A composition according to claim 1 which contains 0.1 to 5% by weight of compound of formula (I).
8. A shampoo composition which facilitates the combing out of the hair when wet or dry and which imparts hold, softness, shine, suppleness, manageability and antistatic properties to the hair when dry, said composition comprising, in an aqueous medium, at least one bis-(quaternary ammonium) derivative having the formula: ##STR25## in which R1, R2, R4 and R5 are identical or different and denote lower alkyl or lower hydroxyalkyl radicals, R3 denotes an alkyl, cycloalkyl, alkenyl, hydroxyalkyl or aralkyl radical containing a maximum of 20 carbon atoms, A1 and A2, which are identical or different, denote alkylene or arylene radicals containing a maximum of 20 carbon atoms, Z denotes --SO2 --, R6 and R7, which are identical or different, represent hydrogen atoms or lower alkyl radicals, and X.sup.⊖ denotes an inorganic or organic anion of a low molecular weight acid, said bis-(quaternary ammonium) derivative being present in an amount of 0.01 to 10% by weight of said composition; and at least one anionic, non-ionic or amphoteric surface active agent or a mixture thereof, said surface-active agent being present in an amount ranging from 2 to 50% by weight of said shampoo composition.
9. A composition according to claim 8, in which R1, R2, R4 and R5 denote a methyl or ethyl radical.
10. A composition according to claim 8 in which R3 denotes a C8 to C18 alkyl radical.
11. A composition according to claim 8 in which A1 and A2 denote an ethylene or trimethylene radical.
12. A composition according to claim 8 which also contains a cationic surface-active agent.
13. A rinsing composition which facilitates the combing out of the hair when wet or dry and imparts hold, softness, shine, suppleness, manageability and antistatic properties to the hair when dry, which comprises, in an aqueous, alcoholic, or aqueous-alcoholic medium, at least one bis-(quaternary ammonium) derivative having the formula: ##STR26## in which R1, R2, R4 and R5 are identical or different and denote lower alkyl or lower hydroxyalkyl radicals, R3 denotes an alkyl, cycloalkyl, alkenyl, hydroxyalkyl or aralkyl radical containing a maximum of 20 carbon atoms, A1 and A2, which are identical or different, denote alkylene or arylene radicals containing a maximum of 20 carbon atoms, Z denotes --SO2 --, R6 and R7, which are identical or different, represent hydrogen atoms or lower alkyl radicals, and X.sup.⊖ denotes an inorganic or organic anion of a low molecular weight acid, said bis-(quaternary ammonium) derivative being present in an amount of 0.01 to 10% by weight of said composition and said composition being in the form of a lotion, cream or gel having a pH ranging from 2 to 11.
14. A composition according to claim 13 which further contains an animal, mineral, vegetable or synthetic oil or wax.
15. A composition according to claim 13 which further contains an anionic, cationic, non-ionic or amphoteric resin.
16. A composition according to claim 13 which further contains a fatty alcohol.
17. A composition according to claim 13 which further contains a polyethyleneglycol or derivative thereof.
18. A composition according to claim 13 which further contains an effective amount of a hair restructuring agent.
19. Process for treating hair, skin or nails, which comprises applying thereto a composition as defined in claim 1.
20. A process according to claim 19 which further comprises allowing said composition to remain on said hair, skin or nails for 1 to 30 minutes and rinsing said hair, skin or nails.
US07/207,624 1980-06-06 1988-06-16 Compositions containing bis-(quaternary ammonium) derivatives for the treatment of keratin materials and natural non-keratin or synthetic textile materials Expired - Fee Related US4828819A (en)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
FR8012687 1980-06-06
FR8012687A FR2483777A1 (en) 1980-06-06 1980-06-06 Conditioning compsns. for hair, textiles, etc. - contg. bis-quat. ammonium cpds., including new cpds.
FR8018711A FR2489324A1 (en) 1980-08-28 1980-08-28 Conditioning compsns. for hair, textiles, etc. - contg. bis-quat. ammonium cpds., including new cpds.
FR8018711 1980-08-28

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WO1993015709A1 (en) * 1992-02-10 1993-08-19 Etheredge Robert W Iii Prophylaxis for keratinous materials
US5780064A (en) * 1997-09-12 1998-07-14 Babson Bros. Co. Germicidal compositions for the treatment of animal infectious diseases of the hoof
US6527814B1 (en) 1996-09-06 2003-03-04 L'oreal S.A. Oxidation dye composition for keratin fibers, comprising an anionic amphiphilic polymer
US20060075581A1 (en) * 1996-07-23 2006-04-13 L'oreal S.A. Oxidation dye composition for keratin fibers comprising a nonionic amphiphilic polymer
WO2007056284A2 (en) * 2005-11-07 2007-05-18 Stepan Company Polycationic viscoelastic compositions

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GB2124645B (en) * 1982-07-30 1986-04-23 Procter & Gamble Shampoo compositions
DE3639885A1 (en) * 1986-11-21 1988-06-01 Benckiser Gmbh Joh A CLEANER WITH DISINFECTING EFFECT
DE4003907A1 (en) * 1990-02-09 1991-08-14 Schwarzkopf Gmbh Hans 5-Tri:fluoromethyl-1,3-di:aminobenzene(s) as hair colourant - have good stability to heat and light, and are compatible with other colourants for shade modification
DE19503279C2 (en) * 1995-02-02 1998-11-12 Henkel Kgaa Cation and / or amphooligomers
GB2312444A (en) * 1996-04-27 1997-10-29 R & C Products Pty Ltd Keratin fibre modification using quaternary ammonium compounds
FR2833835B1 (en) * 2001-12-21 2004-01-30 Oreal COMPOSITION FOR THE OXIDATION STAIN OF KERATINOUS FIBERS COMPRISING AN OXYALKYLENE CARBOXYLIC ETHER ACID, A MONO-OR POLY-GLYCEROL SURFACTANT AND A NON-IONIC OXYALKYLENE SURFACTANT
FR2833836B1 (en) * 2001-12-21 2004-01-30 Oreal COMPOSITION FOR OXIDATION DYEING OF KERATINIC FIBERS COMPRISING AN OXYALKYLENE CARBOXYLIC ETHER ACID AND A QUATERNIZED FATTY CHAIN CELLULOSE
FR2833834B1 (en) * 2001-12-21 2004-01-30 Oreal COMPOSITION FOR KERATIN FIBER OXIDATION STAIN COMPRISING OXYALKYLENE CARBOXYLIC ETHER ACID, MONO-OR POLY-GLYCEROL SURFACTANT AND UNSATURATED FATTY ALCOHOL
FR2833833B1 (en) * 2001-12-21 2004-01-30 Oreal COMPOSITION FOR KERATIN FIBER OXIDATION DYE COMPRISING OXYALKYLENE CARBOXYLIC ETHER ACID, ASSOCIATIVE POLYMER, AND UNSATURATED FATTY ALCOHOL
US8785370B2 (en) * 2007-10-05 2014-07-22 Keratin Complex Holdings, Inc. Reactive keratin protein formulations and methods of using for revitalizing hair
AU2016318280B2 (en) * 2015-09-08 2019-08-15 Kao Germany Gmbh Process for semipermanent straightening and permanent shaping hair
CN110627688B (en) * 2019-09-29 2021-11-30 安徽大学 Carbonamide gemini cationic surfactant and preparation method and application thereof

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WO1993015709A1 (en) * 1992-02-10 1993-08-19 Etheredge Robert W Iii Prophylaxis for keratinous materials
US20060075581A1 (en) * 1996-07-23 2006-04-13 L'oreal S.A. Oxidation dye composition for keratin fibers comprising a nonionic amphiphilic polymer
US7175674B2 (en) 1996-07-23 2007-02-13 L'oreal S.A. Oxidation dye composition for keratin fibres comprising a nonionic amphiphilic polymer
US6527814B1 (en) 1996-09-06 2003-03-04 L'oreal S.A. Oxidation dye composition for keratin fibers, comprising an anionic amphiphilic polymer
US5780064A (en) * 1997-09-12 1998-07-14 Babson Bros. Co. Germicidal compositions for the treatment of animal infectious diseases of the hoof
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US7772165B2 (en) 2005-11-07 2010-08-10 Stephan Company Polycationic viscoelastic compositions
WO2007056284A3 (en) * 2005-11-07 2007-06-28 Stepan Co Polycationic viscoelastic compositions
WO2007056393A3 (en) * 2005-11-07 2007-07-05 Stepan Co Polycationic viscoelastic compositions
US20080248976A1 (en) * 2005-11-07 2008-10-09 Paul Knox Polycationic viscoelastic compositions
WO2007056284A2 (en) * 2005-11-07 2007-05-18 Stepan Company Polycationic viscoelastic compositions
US20080255009A1 (en) * 2005-11-07 2008-10-16 Paul Knox Polycationic viscoelastic compositions
WO2007056393A2 (en) * 2005-11-07 2007-05-18 Stepan Company Polycationic viscoelastic compositions
US20100311622A1 (en) * 2005-11-07 2010-12-09 Paul Knox Polycationic Viscoelastic Compositions
US7879769B2 (en) 2005-11-07 2011-02-01 Stepan Company Polycationic viscoelastic compositions
US7884057B2 (en) 2005-11-07 2011-02-08 Stepan Company Polycationic viscoelastic compositions
US7947633B2 (en) 2005-11-07 2011-05-24 Stepan Company Polycationic viscoelastic compositions
EP2325278A1 (en) * 2005-11-07 2011-05-25 Stepan Company Polycationic viscoelastic compositions
US20110190530A1 (en) * 2005-11-07 2011-08-04 Paul Knox Polycationic Viscoelastic Compositions
US8222455B2 (en) 2005-11-07 2012-07-17 Stepan Company Polycationic viscoelastic compositions

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CA1175609A (en) 1984-10-09
IT8167776A0 (en) 1981-06-05
GB2077589B (en) 1984-08-30
US4774075A (en) 1988-09-27
GB2077589A (en) 1981-12-23
DE3122482A1 (en) 1982-04-08
IT1144597B (en) 1986-10-29

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